Patent GB-851564-A (GB)
Title: Improvements in or relating to primary amines of the heterocyclic series
IPC: C07D277/38
Filed: 1958-05-29
Abstract: The invention comprises sulphones of the formula: <FORM:0851564/IV(b)/1> where X is nitrogen, CH, C-alkyl, C-CF3, C-Ph, C-(methylphenyl), C-(ethylphenyl), C-(dimethylphenyl) or C-(halogenophenyl) and R represents a C1-4 alkyl or alkenyl radical optionally substituted by halogen (including fluorine), hydroxy or cyano.  The compounds are prepared by alkylating or alkenylating a compound of the formula:  <FORM:0851564/IV(b)/2> where "acyl" represents -CO-alkyl, -CO-O-alkyl or -SO2-aryl, with an R-halide, a sulphonic acid R-ester, a halogen-R-carboxylic acid (if desired, with simultaneous or subsequent decarboxylation), acrylonitrile or vinyl chloride, oxidising the 5-RS-compound to the corresponding 5-R-O2S-compound with H2O2, permanganate or hypochlorite, and de-acylating the latter product by acid or alkaline hydrolysis. Hydroxy groups in the radical R may be replaced by chlorine by reaction with phosphorus oxychloride or thionyl chloride, or may be removed as water to provide a double bond.  Carboxyl groups in the radical R are replaced by H or Cl by decarboxylation at the de-acylation stage or chlorination preceding the oxidation stage, respectively; alpha-hydrogen atoms may also be replaced by chlorine during this latter stage. 2-Amino-5-cyanoethylsulphonothiazole may also be prepared by reacting 2-aminothiazole-5-sulphinic acid with acrylonitrile.  2 - Acetylamino - 5 - methylmercapto - 1 - thio - 3 : 4-diazole is prepared by refluxing dithiocarbazinic acid methyl ester with acetylisothiocyanate.  The compounds of the first general formula may be diazotised and the resulting 2-diazo derivatives coupled with azo components to give dyestuffs.ALSO:Mono- and disazo dyestuffs of the formula:  <FORM:0851564/IV (c)/1> where X is nitrogen, CH, C-alkyl, C-CF3, C-Ph, C-(methylphenyl), C-(ethylphenyl), C-(dimethylphenyl) or C-(halogenophenyl), R represents a C1-4 alkyl or alkenyl radical optionally substituted by halogen (including fluorine), hydroxy or cyano, Y represents hydrogen, halogen, alkyl, alkoxy, trifluoromethyl, trifluoroacetyl or C1-18 alkanoylamino, R1 represents a C1-4 divalent aliphatic radical, R2 represents a hydroxyalkyl, dihydroxyalkyl, alkoxyalkyl, acetoxyalkyl, cyanoalkyl, difluoromethyl, trifluoromethyl, fluorinated cyanoalkyl, carbalkoxyalkyl or carbamic acid alkyl ester radical, n is 1 or 2, M represents hydrogen, hydroxyl, optionally-substituted acetoxy, alkoxy or a carbamic acid alkyl ester radical, when n is 1, and for a single carbon to nitrogen linkage when n is 2, and Z represents hydrogen, halogen, alkyl, alkoxy or, together with N-CH2-R2 and the vicinal benzene nucleus, a tetrahydroquinoline ring, are prepared by diazotizing compounds of the formula:  <FORM:0851564/IV (c)/2> and coupling the products with azo components of the formula:  <FORM:0851564/IV (c)/3> The dyes can be applied from aqueous suspension to polyamide fibres (e.g. nylon), polyethylene terephthalate fibres, cellulose acetate and triacetate fibres and polyvinyl fibres, to which they impart brilliant red and violet shades.  They may also be used for colouring lacquer media, oils, plastics and artificial fibres in the mass.  Specification 728,969 is referred to.